KR20060041173A - Ink for spacer formation - Google Patents

Abstract

In the method of spacer formation using a printing system, it is intended to improve the adherence between spacer particles and a binder resin. There is provided an ink for spacer formation that can be employed in the printing method. This ink contains a resin composition comprising spacer particles (A) and a thermosetting or active energy ray curable resin for spacer particle dispersion (C).

Description

Ink for Spacer Formation {INK FOR SPACER FORMATION}

The present invention relates to an ink for forming a spacer.

Japanese Patent Application Laid-Open No. 2000-35582 discloses a method of forming a spacer by gravure offset printing. In Japanese Patent Laid-Open No. 2000-35582, Claims 2 and 3 describe the use of an ink in which 20 to 60% by weight of a spherical spacer is blended in a resin having a viscosity of 2000 to 25000 cps. And polyester-based resin are shown.

Japanese Patent Application Laid-Open No. 11-323220, Japanese Patent Application Laid-Open No. 9-111170, and Japanese Patent Application Laid-Open No. 7-110404 are heat-curable inks suitable for forming a color filter layer or black matrix by concave plate offset printing. It is described that polyester-melamine resin, epoxy melamine resin, etc. are used.

In addition, Japanese Patent Laid-Open No. 2000-347191 discloses a method of forming a spacer by an inkjet printing method. In Japanese Patent Laid-Open No. 2000-347191, Claim 1 describes that the spacer contains formed solid fine particles and a binder resin.

In Japanese Patent Laid-Open No. 2000-35582, only a viscosity is specified with respect to resin. The polyester resin is shown in the Example and only the particle diameter of the resin spacer bead is prescribed | regulated.

In Japanese Patent Application Laid-Open No. 11-323220, Japanese Patent Application Laid-Open No. 9-111170, and Japanese Patent Application Laid-Open No. 7-110404, a polyester resin is used as a binder resin of an ink used in the concave plate offset printing method of a color filter. Melamine resin, melamine modified polyester resin, epoxy melamine resin, melamine modified epoxy resin, etc. are used. However, besides the resin, high boiling point solvents such as ketones such as higher alcohols, ethylene glycol ethers, propylene glycol ethers, cyclohexanone and isophorone are used. For this reason, after printing, long time drying at high temperature is necessary, and when heating is inadequate, a solvent remains and it becomes a cause of liquid crystal contamination. In addition, when the adhesion between the spacer, the ink, and the alignment film is poor after curing, the spacer moves due to the interfacial separation between the spacer and the binder resin and the adhesion failure between the spacer and the binder resin during rubbing or vibration of the alignment film. There was a problem such as scratches.

Together with Japanese Patent Application Laid-Open No. 2000-35582 and Japanese Patent Application Laid-Open No. 2000-347191, the formation of chemical bonds at the interface between the binder resin and the spacer particles is not described. However, if no chemical bond is formed at the interface between the binder resin and the spacer particles, when external force such as vibration is applied, the spacer particles cause interfacial separation from the binder resin, and the separated spacer particles move to damage the alignment film, so that the light after impact There was a problem such as loss.

The subject of this invention is making it possible to improve the adhesiveness of a spacer particle and binder resin in the spacer formation method by a printing system.

The present invention is an ink for forming a spacer used in a printing method,

A: spacer particles, and

C: It is characterized by containing a thermosetting or active energy ray-curable resin mixture for dispersing the spacer particles.

According to the present invention, the spacer particles are dispersed in the thermosetting or active energy ray-curable resin mixture (C), and the resin mixture (C) has a component containing a functional group capable of chemically reacting with the spacer particles. New chemical bonds can be created between them to improve adhesion. Moreover, in preferable embodiment, a new chemical bond is produced | generated also between binder resin and an oriented film, As a result, the adhesiveness of a spacer and an oriented film can be improved.

1 (a) and 1 (b) are schematic diagrams showing the bonding patterns of the spacer particles (A), the resin (B) and the alignment film, respectively.

2 (a) and 2 (b) are schematic diagrams showing bonding patterns of spacer particles (A), resins (B, F, G), monomers, and alignment films.

Each requirement of the present invention will be described in more detail below.

(Print method)

Printing methods include plate printing methods and plateless printing methods.

The plate printing method means a printing method using a plate, and the following method can be exemplified.

(1) Convex plate printing (direct printing method, offset method)

(2) Concave plate printing or gravure printing (transfer method, offset method, pad method)

(3) flat printing or offset printing

(4) stencil printing or screen printing

The plateless printing method is not limited as long as the printing method does not use a plate, but includes an inkjet printing method and a laser printing method. Typical inkjet printing methods include the following.

(1) bubble jet method

(2) Piezo method

In a preferred embodiment, the resin mixture (C) contains at least one component containing a functional group capable of chemically reacting with the particles (A). This component may be a thermosetting, active energy ray-curable resin (B), or may be any component such as another resin, a monomer to a diluent, an oligomer, an optical radical initiator, or a solvent.

For example, in preferable embodiment, the component containing the functional group which can chemically react with particle | grain (A) is 1 type, or 2 or more types of resin (B). In this case, as shown schematically in Fig. 1 (a), the functional groups (a, a ', a ") of the spacer particles (A) and the functional groups (b, b', b") of the resin (B) are React and bind.

In more preferable embodiment, the component containing the functional group which can chemically react with particle | grain (A) is 1 type or 2 or more types of resin (B), and resin (B) can react with the functional group of an oriented film. In this case, as shown schematically in Fig. 1 (b), the functional groups (a, a1, a ", a1") of the spacer particles (A) and the functional groups (b1, b1 ") of the resin (B) react. At the same time, the resin (B) reacts with the functional group of the alignment film to bond.

Moreover, in another preferable embodiment, the resin mixture (C) contains the some kind of resin (B). The resin (B) chemically reacts with the spacer particles (A), the other resin (F) chemically reacts with the resin (B), and also with the functional group of the alignment film. For example, in the example shown schematically in Fig. 2 (a), the functional group (b ') of the resin (B) reacts with the functional group (a') of the spacer particles (A), and the resin (F) is a resin (B). ) And the resin (F) react with the resin (G). In addition, resin (F) reacts with the functional group of an oriented film. As a result, the spacer particles (A) and the alignment layer are chemically bonded through the produced polymer compound.

In another preferred embodiment, components other than the resin in the resin mixture react with the resin (B) and also with the functional group of the alignment film. For example, in the example shown schematically in FIG. 2 (b), the functional group (b ') of the resin (B) reacts with the functional group (a') of the spacer particles (A), and the monomer or diluent reacts with the resin (B). And the particle (A), and the monomer reacts with the functional group of the alignment film. As a result, the spacer particles (A) and the alignment layer are chemically bonded through the produced polymer compound.

In a preferred embodiment, the resin (B) has a functional group (b) that can react by heating, and the particles (A) have a functional group (a) that can react with the functional group (b). As a result, the spacer particles and the binder resin are integrated by the reaction between the spacer particles and the functional group of the binder resin, thereby eliminating the detachment of the spacer particles.

As a functional group (b) of this resin (B), a hydroxyl group, an epoxy group, a carboxyl group, a hydrolyzable silyl group, a silanol group, an isocyanate group, a metyrol group, an alkylated methirol group, an imino group, an acid anhydride, and an unsaturated group can be illustrated. These functional groups are selected based on the reactivity with the functional group (a) which particle | grains (A) have.

Moreover, in resin mixture (C), two or more types of particle | grains (A) and reactive resin (B) can be contained, or a hardening | curing agent and a coupling agent can be mix | blended. As this example, the combination of a polyester resin, a melamine resin, an epoxy resin, a melamine resin, an epoxy resin, an amine-type hardener, etc. are mentioned.

As a functional group which can react with the component in the resin compound which particle | grains (A) have, a silanol group, a carboxyl group, an epoxy group, a hydrolyzable silyl group, an isocyanate group, an unsaturated group, a methrol group, an alkylated metyrol group, an imino group, an acid anhydride, An amino group can be illustrated.

In preferable embodiment, the functional group (b) which can react by the heating which resin (B) has is the functional group (b1) which can react with the functional group which remain | survives in an oriented film.

Thereby, the adhesiveness of binder resin and an orientation film improves by reaction between the functional group (b1) of binder resin, and the functional group which remain | survives in an orientation film.

As a functional group which remain | survives in an oriented film, a carboxyl group and an amide group can be illustrated, but a carboxyl group is especially preferable at a reactive point.

Moreover, as a functional group (b1) which can react with the functional group which remain | survives in an oriented film, an epoxy group, a hydroxyl group, and an amino group can be illustrated, An epoxy group is especially preferable at the point of reactivity.

In preferable embodiment, the functional group (b1) of resin (B) is an epoxy group, and the said functional group (a) of particle | grains (A) is a functional group (a1) which can react with an epoxy group. As this functional group (a1), an epoxy group, a hydroxyl group, a silanol group, etc. are mentioned.

Moreover, in preferable embodiment, resin (B) has the functional group (b ') which can react with active energy ray, and particle | grain (A) has the functional group (a') which can react with functional group (b '). As this functional group (b '), unsaturated groups, such as an acryl group and a methacryl group, can be illustrated.

Moreover, as functional group (a ') of particle | grain (A), unsaturated groups, such as an acryl group and a methacryl group, can be illustrated.

In a preferred embodiment, the resin mixture (C) contains a component having a functional group (b1 ') capable of reacting with a functional group remaining in the alignment film. This component may be resin (B), resin other than resin (B) may be sufficient, and other components, such as a monomer, an oligomer, a diluent, a photoinitiator, may be sufficient as it. An epoxy group can be illustrated as a functional group (b1 ').

In a preferred embodiment, the ink has a diluent (D) and / or a photo radical initiator (E) having a functional group (a ') capable of reacting with an active energy ray or a functional group capable of reacting with a functional group (b'). .

In a preferred embodiment, the resin (B) has a functional group (b ″) capable of cationic polymerization by heating and / or energy rays, and the functional group (a ″) in which the particles (A) can react with the functional group (b ″). Have

An epoxy group and a hydroxyl group can be illustrated as this functional group (b "). Moreover, an epoxy group and a hydroxyl group can be illustrated as a functional group (a") of particle | grain (A).

In a preferred embodiment, the functional group (b ") of the resin (B) is a functional group (b1") which can react with the functional group remaining in the alignment film. As this functional group (b1 "), an epoxy group and a hydroxyl group can be illustrated.

In more preferable embodiment, the functional group (b1 ") of resin (B) is an epoxy group, and the functional group (a") of particle | grains (A) is a functional group (a1 ") which can react with an epoxy group. This functional group (a1") As an epoxy group, a hydroxyl group can be illustrated.

Moreover, in this embodiment which cationically polymerizes resin, the resin composition has the diluent (H) and / or the photocationic initiator (I) which have a functional group which can react with a functional group (a ") or a functional group (b"). .

In order to make the ink of this invention suitable for the printing system, the quantity of solvent and the kind of solvent in a resin mixture (C) can be suitably experimentally determined. The solvent in the resin mixture (C) may dissolve other components in the resin mixture (C), or may disperse other components.

As for the ink used for the plate printing method of this invention, it is preferable that the content of a solvent is small, 30 weight% or less is specifically preferable, and 10 weight% or less is more preferable. In especially preferable embodiment, the ink used for the plate printing method of this invention does not contain a solvent substantially. This means that the solvent component is not actively added to the ink, and trace amounts of the solvent and unavoidable impurities are excluded.

Thus, since ink does not contain a solvent substantially, liquid crystal contamination by the residual solvent after spacer formation is eliminated, and further stable printing is attained. In particular, the subsequent heating step can be omitted by using the active energy ray curable resin.

Moreover, polar solvents, such as alcohol type, a glycol type | system | group, a propylene glycol type | system | group, and water, can be illustrated to the ink used for the inkjet printing method of this invention as a solvent.

Hereinafter, each component of the ink of this invention is further described.

(Spacer particles)

The spacer particle used for this invention is not limited. In preferable embodiment, it is particle | grains obtained by the precipitation polymerization method or the seed polymerization method. The precipitation polymerization method is a polymerization method in which a monomer is dissolved and a polymer based on the monomer is polymerized in the solvent in which the monomer is not dissolved to precipitate polymer particles. The seed polymerization method is a method of obtaining secondary polymer particles by swelling the polymer particles obtained by the precipitation polymerization method with a monomer, polymerizing the monomer again with a radical embedded in the polymer particles.

In the precipitation polymerization and the seed polymerization, crosslinked polymer particles using polyvalent vinyl compounds such as divinylbenzene, diallyl phthalate and tetraaryloxyethane are preferable as part of the monomer. The crosslinked polymer particles have good solvent resistance and heat resistance. In the above-mentioned precipitation polymerization and seed polymerization, particles having a suitable spherical shape and uniform particle size distribution as a liquid crystal spacer are obtained. Particularly, in seed polymerization, spherical particles having a large particle size are obtained.

In the present invention, in addition to the particles, polymer particles, glass particles, ceramic particles, metal particles, and the like polymerized by other polymerization methods may be used. As the liquid crystal spacer, the particles are spherical and the particle size distribution is uniform. One is preferable.

By forming an adhesion layer on these particles, functional groups as described later can be introduced into the surface of the particles.

Examples of the material used as the adhesion layer include methyl acrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate and methyl meth. Acrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, iso-butyl vinyl ether, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride Having a thermoplastic as a homopolymer of a polymerizable monomer such as ethylene, propylene, isoprene, chloroprene, butadiene, or two or more copolymers of the monomer. Will.

These thermoplastic polymers or copolymers are softened by heating to show good adhesion to the surface of the orientation substrate. Moreover, as a material of an adhesion layer, homopolymer of epoxy group containing monomers, such as glycidyl acrylate, glycidyl methacrylate, glycidyl allyl ether, and an acrylate or methacrylate containing an alicyclic epoxy group, or the said epoxy group containing Epoxy-group containing polymers, such as a copolymer of 2 or more types of monomers or a copolymer of an epoxy group containing monomer and monomers other than the said epoxy group containing monomer, and a functional group which has affinity to glass surfaces, such as polyvinyl alcohol, or a polyimide coated glass surface Polymers are also used. Polyvinyl alcohol is obtained by polymerizing vinyl acetate and then hydrolyzing it.

In a preferred embodiment, in the spacer particles, the particle surface and the polymer constituting the adhesion layer are bonded by covalent bonding. As the method, a graft polymerization method and a polymer reaction method can be illustrated. In the graft polymerization method, a method of introducing a polymerizable vinyl group to the particle surface, polymerizing the monomer with the vinyl group as a starting point, a method of introducing a polymerization initiator to the particle surface, and polymerizing the monomer by the initiator. Two things are considered.

(1) Vinyl group introduction method

In the vinyl group introduction method, a vinyl group is introduced by reacting a monomer having a functional group capable of reacting covalently by reacting with a functional group such as a hydroxyl group, a carboxyl group, an epoxy group, a silyl group, a silanol group, and an isocyanate group on the particle surface. do.

(2) Initiator introduction method

An initiator is introduce | transduced by making the said functional group exist in a particle surface, and reacting initiators, such as a peroxide, a peroxide, an azo compound, which have a functional group which can covalently bond with the said functional group.

(3) Method to make functional group exist on surface

When the particles are produced by the precipitation polymerization or the seed polymerization, polar solvents such as alcohols such as methanol, ethanol, iso-propanol, sec-propanol and t-butanol, ketones such as acetone and methyl ethyl ketone are used as the solvent. And the monomer mixture containing the monomer which has the said functional group is polymerized. The particles produced by such polymerization orient the functional groups on the surface. Examples of the monomer having the functional group include the following ones. Examples of the carboxyl group-containing monomers include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride and citraconic acid. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, allyl alcohol and the like. Examples of the epoxy group-containing monomers include glycidyl acrylate, glycidyl methacrylate and glycidyl allyl ether. As a methirol group containing monomer, N-metholacrylamide, N-metholol methacrylamide, etc. are mentioned. Examples of the amino group-containing monomers include dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate. Examples of the acid amide group-containing monomers include acrylamide and methacrylamide. Examples of the silyl group-containing monomer include γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, p-trimethoxysilylstyrene, p-triethoxysilylstyrene, p-trimethoxysilyl-α-methylstyrene, p-triethoxysilyl-α-methylstyrene, γ-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl-γ-aminopropyl) trimethoxysilane Hydrochloric acid;

Moreover, as a method of introducing a silyl group, the method of making silane gas react with the particle | grains which have functional groups which have active hydrogen, such as a silanol group, a hydroxyl group, a carboxyl group, on the surface is also applied.

In addition to the polymer particles, in the case of inorganic particles such as glass, ceramics and metals, for example, γ- (2-aminoethyl) aminopropylmethyldisilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, The silyl group is treated by treating with a silane coupling agent such as γ-glycidoxy propylpropyl silane, γ-mercapto propyl trimethoxy silane, methyl trimethoxy silane, p-trimethoxy silyl styrene, methyl trichlorosilane, and the like. Can be introduced to the surface.

The polymer particle or inorganic particle which introduce | transduced the said silyl group into the surface becomes a particle which has a silanol group on the surface by hydrolyzing a silyl group by alkali or acid treatment.

Examples of the active energy curable resin include urethane acrylate oligomers in which an acrylate group is bonded to an oligomer having a polyurethane structure, polyester acrylate oligomers in which an acrylate group is bonded to an oligomer having a polyester structure, and an acrylate group in an oligomer having an epoxy group. Bonded epoxy acrylate oligomer, urethane methacrylate oligomer having methacrylate group bonded to oligomer having polyurethane structure, polyester methacrylate oligomer having methacrylate group bonded to oligomer having polyester structure, oligomer having epoxy group Epoxy methacrylate oligomers having a methacrylate group bonded thereto, a polyurethane acrylate having an acrylate group, a polyester acrylate having an acrylate group, and an acrylate group The epoxy acrylate resin which has, the polyurethane methacrylate which has a methacrylate group, the polyester methacrylate which has a methacrylate group, the epoxy methacrylate resin which has a methacrylate group, etc. are mentioned.

The radical radical initiator (photoinitiator) (E) which can be mixed with an active energy ray curable resin composition generate | occur | produces a radical by light. It is preferable to start radical polymerization of an unsaturated group containing polymer, a monofunctional, and a polyfunctional monomer, and all the radical reaction type photoinitiators conventionally well-known in the photosensitive resin field can be used, and are not specifically limited. For example, benzophenone, acetophenone, benzoin, benzoin isobutyl ether, benzoin isopropyl ether, benzoin ethyl ether, 2,4-dimethyl thioxanthone, 2-chlorothioxanthone, ethyl anthraquinone, 4 , 4'-bisdimethylaminobenzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal and the like. These photoinitiators can be used individually or in combination of 2 or more types according to the type of hardening | curing agent (crosslinking agent) and diluent to be used.

The usage-amount of a photoinitiator is not specifically limited, Usually, it is used in the ratio of about 0.01-10 weight part per 100 weight part of active energy ray curable resin bridge | crosslinked by ionizing radiation, such as an ultraviolet-ray or an electron beam.

As the diluent (D) which can be mixed into the active energy ray-curable resin composition, a compound having at least one polymerizable carbon-carbon unsaturated bond can be used. Specifically, 1 type, or 2 or more types of the following monomers can be used: allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate , 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, isodecyl acrylate, isooctyl acrylate, Uryl acrylate, 2-methoxyethyl acrylate, methoxy ethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacryl Rate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethyrolpropanediacrylate, glycerol diacrylate, tripropylene glycol diacrylate, glycerol triacrylate, trimetholpropane triacrylate, polyoxyethyl Trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimetholpropane triacrylate, butylene glycol diacrylate, 1,2, 4-butane triol triacrylate, 2,2,4-trimethyl-1,3-pentanediol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, dipentaerythritol hexaacrylate, etc. Acrylates and methacrylates in which the acrylate group is substituted with a methacrylate group; γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone, 2-hydroxyethylacryloyl phosphate, tetrahydrofurfuryl acrylate, dicyclopentenyl acrylate, dicyclopentenyl oxy Ethyl acrylate, 3-butanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, hydroxy pivalic acid ester neopentyl glycol diacrylate, phenol ethylene oxide modified acrylate, phenol propylene oxide modified acrylic Latex, N-vinyl-2-pyrrolidone, bisphenol A-ethylene oxide modified diacrylate, pentaerythritol diacrylate monostearate, tetraethylene glycol diacrylate, polypropylene glycol diacrylate, trimetholpropane propylene Oxide modified triacrylate, isocyanuric acid ethylene oxide modified triac Acrylate monomers such as acrylate, trimetholpropane ethylene oxide modified triacrylate, pentaerythritol pentaacrylate, pentaerythritol hexaacrylate, pentaerythritol tetraacrylate, and methacryl substituted with these acrylate groups with methacrylate groups Rate.

Moreover, from a viewpoint of adhesiveness with an oriented film, it is preferable that a diluent (D) has an epoxy group. As an example, 3, 4- epoxycyclohexyl methyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, glycidyl (meth) acrylate, etc. are mentioned.

The usage-amount of a diluent is not specifically limited, Usually, it is used in the ratio of 1-200 weight part per 100 weight part of active energy ray curable resin.

(Heat curable resin)

Examples of the thermosetting resin include epoxy resins (curing agents such as amines, polyamides and acid anhydrides), polyester resins and melamine resins, epoxy resins and melamine resins.

Specific examples of the epoxy resin include the following: hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, phenyl diglycidyl ether, phenol novolac type epoxy resin, Cresol novolac type epoxy resin, trishydroxy phenylmethane type epoxy resin, dicyclopentadiene dimethanol type epoxy resin, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-S type epoxy resin, 2,2- Epoxy compound of bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, hydrogenated bisphenol-A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type Epoxy Resin, Epoxy Compound of Hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, Brominated Bisphenol-A Epoxy Resin, Brominated Bisphenol-F Epoxy Resin, Cyclohexanedimethanol diglycidyl Ether compound, 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, diethylene glycol diglycidyl ether, polysulfide diglycidyl ether, biphenol type epoxy resin, bisphenol -A novolak type epoxy resin, naphthalene skeleton containing epoxy resin, heterocyclic epoxy resin.

Moreover, in addition to said epoxy resin, alicyclic epoxy resin and oxetane resin are preferable. An alicyclic epoxy resin is an oxide which has an oxirane ring obtained by making peracetic acid react with the cyclic aliphatic unsaturated compound which has two or more unsaturated groups, The epoxy resin of the type which epoxidized the double bond of the cyclohexene ring is typical, and It is preferable to have 2 or more epoxy groups in 1 molecule. Specifically, For example, 3, 4- epoxycyclohexyl methyl; 3 ', 4'- epoxycyclohexane carboxylate (trade name UVR6110 and U VR6105 made by UCC Corporation, brand name CELLOXIDE2021 made by Daicel Kagaku Co., Ltd.), bis (3, 4- epoxycyclohexyl methyl) adipate (product made by UCC Corporation) UVR6128 etc.), (epsilon) -caprolactone modified 3, 4- epoxycyclohexylmethyl; 3 ', 4'- epoxycyclohexane carboxylate (trade name CELLOXIDE2081 made from Daicel Kagaku Co., Ltd.), 1-methyl-4- (2-methyloxyranyl) -7-oxabicyclo [4.4.0] Heptane (trade name CELLOXIDE3000 by Daicel Kagaku Co., Ltd.) can be used preferably. These can be used individually or in combination of 2 or more types.

An oxetane compound is a compound which has 1 or more oxetane ring in a molecule | numerator. Specifically, 3-ethyl-3-hydroxymethyl oxetane (trade name: OXT101 manufactured by Doagosei Co., Ltd.), 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene ( Copper OXT121 etc.), 3-ethyl-3- (phenoxymethyl) oxetane (such as copper OXT211), di (1-ethyl-3-oxetanyl) methyl ether (such as copper OXT221), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (such as copper OXT212) can be preferably used, and 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane And di (1-ethyl-3-oxetanyl) methyl ether can be preferably used. These can be used individually or in combination of 2 or more types.

There is no restriction | limiting in particular in a polymer polyol. For example, at least one polyether polyol selected from polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like, at least one polyester polyol, hexamethylene carbonate and penta selected from esters of polyhydric alcohols and polybasic acids. At least one polycarbonate polyol selected from methylene carbonate, polycaprolactone polyol and at least one polylactone polyol selected from polybutylolactone polyol are preferred.

One kind can be selected from these polyether polyol, polyester polyol, polycarbonate polyol, and polylactone polyol, or multiple types can be combined.

As melamine resin, amino resin, such as a methyl ether melamine resin, a butyl ether melamine resin, an isobutyl ether melamine resin, a butyl ether benzoguanamine resin, etc. are mentioned, for example, 1 type or 2 of these Papery mixtures can be used. As the amino resin in the present invention, commercially available Niwarak MS-21, MS-11, MW-24, MS-001, MX-002, MX-730, MX-750, MX-708, MX- 706, MX-042, MX-410, Mitsui Cytec's Cymel 370, 771, 325, 327, 703, 712, 715, 701, 202, 207, etc. are mentioned.

A hardening | curing agent and an acidic catalyst can be added to thermosetting resin. As such a hardening | curing agent, an acid anhydride, an amine hardening | curing agent, and a cationic hardening | curing agent can be illustrated.

Specific examples of the acid anhydride curing agent include aromatic carboxylic acids such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol anhydrous trimellitic anhydride, and biphenyltetracarboxylic anhydride. Alicyclic carboxylic acid anhydrides such as anhydrides of aliphatic carboxylic acids such as anhydrides, azeline acid, sebacic acid, and dodecaneic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, nadic anhydride, hetic anhydride and hymic acid anhydride Can be mentioned.

Specific examples of the amine curing agent include diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,5-diaminonaphthalene , aromatic amines such as m-xylylenediamine, aliphatic amines such as ethylenediamine, diethylenediamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, polyetherdiamine, dicyandiamide, Biguanides, such as 1- (o-tolyl) biguanide, are mentioned.

As catalysts, tertiary amines (tris (dimethylaminomethyl) phenol, dimethylbenzylamine, 1,8-diazabicyclo (5,4,0) undecane (DBU)), imidazoles and the like are typical.

As the acid catalyst, acids such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, butyl phosphoric acid, octyl phosphoric acid, and amine neutralization of these acids are preferable.

Cationic Polymerizable Resin

Examples of the cationic polymerization resin include epoxy compounds, oxetane compounds, oxolane compounds, cyclic acetal compounds, cyclic lactone compounds, thiirane compounds, thiethane compounds, vinyl ether compounds, reaction products of epoxy compounds and lactones. Spirolosoester compounds, ethylenically unsaturated compounds, cyclic ether compounds, cyclic thioether compounds, vinyl compounds and the like.

It is preferable to mix a diluent (H) and / or a photocationic initiator (I) with cationic polymerization resin.

As a photocationic polymerization initiator (I), an aryldiazonium salt type compound, a triarylsulfonium salt type compound, a diaryl iodonium salt type compound, etc. are mentioned, for example.

Examples of the diluent (H) include alkylphenol monoglycidyl ether, alkyl monoglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and trimeth. Tyrol propane triglycidyl ether, 1, 6- hexanediol glycidyl ether, etc. are mentioned.

The usage-amount of a photocationic polymerization initiator is not specifically limited, Usually, it is used in the ratio of 0.1-10 weight part per 100 weight part of active energy ray curable resin.

The usage-amount of a diluent is not specifically limited, Usually, it is used in the ratio of 1-40 weight part per 100 weight part of active energy ray curable resin.

Example

Example 1

The spacer particle (A), the resin component (B), and the ultraviolet radical initiator were mixed to prepare an ink. The functional group of the particle (A) is a hydroxyl group, the resin component (B) is an isocyanate group-containing urethane acrylate, and the initiator is 2-hydroxy-2-methyl-1-phenylpropan-1-one `` Darocure 1173 (Cibaga Knight made). This mixture was printed on the filter substrate by the gravure offset printing method described in Japanese Patent Laid-Open No. 2000-35582, and cured to place the spacer on the BM. Specifically, it preheated at 80 degreeC for 10 minutes, and the ultraviolet-ray was continuously irradiated at 1000mj / cm. The evaluation results of the obtained spacers are shown in Tables 1 and 2.

(Assessment Methods)

(Close contact between binder and spacer)

After the ink was cured on the preparat, the preparat was divided to prepare an ink cross section, and the presence or absence of peeling at the binder resin and the spacer interface was observed by a scanning electron microscope. "(Circle)" shows no peeling, "(triangle | delta)" shows partial peeling, and "x" shows complete peeling.

(Adhesion between Ink and Orientation Substrate)

After printing ink on an orientation board | substrate, cellophane tape peeling was performed and the presence or absence of peeling of the printing dot was observed with the optical microscope. "(Circle)" shows no peeling, "(triangle | delta)" shows partial peeling, and "x" shows complete peeling.

(Light loss)

An ITO / polyimide alignment film was formed on the surface, the ink was printed on the substrate subjected to the rubbing treatment so as to be in the form of BM by a printing machine, and heat treatment was performed under predetermined conditions. Then, the sealing compound was printed on the board | substrate periphery, the board | substrate was bonded by the normal method, and STN liquid crystal panel was produced by inject | pouring a liquid crystal (ZLI-2293 (S078W) by Merck company) into a cell.

About the produced liquid crystal panel, the orientation abnormality of the circumference | surroundings of the liquid crystal spacer at the time of lighting was observed and evaluated.

That is, 50V and 1 second DC voltage (DC) was applied to the liquid crystal panel produced by the above method, and the change of the orientation abnormality (light loss state) around the liquid crystal spacer was evaluated before and after application.

"(Circle)" has no light loss, "(triangle | delta)" is a state which can confirm light loss in some parts, and "x" has light loss.

Moreover, "gap deviation" was determined from the panel appearance on the same conditions as the panel produced by the optical loss evaluation.

In this evaluation, "(circle)" has no gap deviation, and "x" has gap gap.

(Liquid crystal contamination)

A predetermined amount of ink cured product and a predetermined amount of LC (ZLI-4792, manufactured by Merck Co., Ltd.) are placed in a sample bottle, and heat accelerated treatment is carried out in a dryer. Resin-cured solids (excluding diluents) are 5% with respect to the liquid crystal. The liquid crystal contamination was measured by heating promotion under the following conditions.

Heat promotion condition: 80 ℃ -7hr

Resistivity measurement DC 20V-5sec Applied resistance value measuring device: Liquid electrode (LE21 manufactured by Ando Denki) High resistance measuring device (Kesray SR-6517)

Evaluation: The difference with a blank ○: Almost none △: Less than one digit, X: More than one digit

(Impact resistance)

The panel produced in "light loss evaluation" was shocked, and subsequent light loss was evaluated.

Table 1

Table 2

As a result, in Example 1, liquid crystal contamination was suppressed.

Example 2

The same spacer particles (A) as in Example 1 were used. The functional group of particle | grains (A) is a hydroxyl group. As the resin component (B), an epoxy resin was used, and as the acid anhydride curing agent, methyltetrahydrophthalic anhydride "Epolite B-570" (manufactured by Dainippon Ink, Inc.) and an aromatic tertiary amine were mixed as a catalyst. This mixture was printed in the same manner as in Example 1, cured, and spacers were placed on BM. Specifically, it was cured by heating at 200 ° C. for 60 minutes.

As a result, the adhesiveness of resin and a spacer particle and the adhesiveness of an ink and an orientation film also improved.

Example 3-1

The same spacer particles (A) as in Example 1 were used. The functional group of particle | grains (A) is a hydroxyl group. As the resin component (B) "Fraccel 410D" (polycaprolactone tetraol: manufactured by Daicel Kagaku Kogyo Co., Ltd.), "Epicoat 1001" (Epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd.), "Simel 303" (melamine resin, Mitsui Manufactured by Scitech Co., Ltd., and paratoluenesulfonic acid were mixed as an acid catalyst. This mixture was printed in the same manner as in Example, cured, and spacers were placed on BM. Specifically, it hardened | cured by heating at 150 degreeC for 30 minutes. As a result, good characteristics were obtained.

Example 3-2

The same spacer particle (A) as Example 7 (synthesis | combination of particle | grains which have an epoxy group in the surface) of Japanese Patent No. 3417681 was used. The functional group of particle | grains (A) is an epoxy group. "E30" (bisphenol A type epoxy resin, product made by Japan epoxy resin) is used as a resin component (B), and "H30" (amine type curing agent of ketimine type, product made by Japan epoxy resin company) is mixed as an amine curing agent. did. This mixture was printed in the same manner as in Example 1, cured, and spacers were placed on BM. Specifically, it hardened | cured by heating at 150 degreeC for 30 minutes. As a result, good characteristics were obtained.

Example 4

The same spacer particles (A) as in Example 1 were used. The functional group of particle | grains (A) is a hydroxyl group. "Epoxide GT403" (polyfunctional alicyclic epoxy resin, manufactured by Daicel Kagaku Kogyo Co., Ltd.) is used as the epoxy resin component (B), and "acid aid SI-100L" (aromatic sulfonium salt compound) is mixed as a polymerization initiator. did. This mixture was printed in the same manner as in Example 1, cured, and spacers were placed on BM. Specifically, it hardened | cured by heating at 150 degreeC for 30 minutes. As a result, good characteristics were obtained.

Example 5

The particle surface was surface-treated with MOI (2-isocyanate ethyl methacrylate, Showa Denko make) and KBM5103 ((gamma) -acryloxypropyl trimethoxysilane, the Shin-Etsu Chemical Co., Ltd.) spacer particle which introduced the unsaturated group (A ) As the resin (B), an ultraviolet ray-curable resin "M305" (pentaerythritol triacrylate: manufactured by Toagosei Co., Ltd.) was used, and a radical photopolymerization initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one) was used. "Darocure 1173" (made by Chiba Kaiki). This mixture was printed in the same manner as in Example 1, cured, and spacers were placed on BM. Specifically, it was cured by irradiating 1000 mj / cm of ultraviolet rays. As a result, good characteristics were obtained.

Example 6

The same spacer particles (A) as in Example 5 were used. As the resin (B), an epoxy group and an unsaturated group-containing phenol novolak resin "ENA" (manufactured by Kagawa Chemical) were used, and as the diluent (D), an ultraviolet curable monomer "M210" (bisphenol A type EO modified diacrylate, Toagosei Co., Ltd.) and the radical photopolymerization initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one) "Darocure 1173" (made by Chiba-Geigi Co., Ltd.) were mixed. This mixture was printed in the same manner as in Example 1, cured, and spacers were placed on BM. Specifically, it was hardened by irradiating 1000mj / cm ultraviolet-ray, and it hardened again by heating at 150 degreeC for 30 minutes. As a result, good characteristics were obtained.

Example 7

The same spacer particles (A) as in Example 5 were used. As the resin (B), an acrylate "M7100" (polyester acrylate, manufactured by Toagosei Co., Ltd.) was used, and as the diluent (D), an ultraviolet curable monomer "4HBAGE" (4-hydroxybutyl acrylate glycidyl ether, Nihon Kasei Co., Ltd.) and the radical photopolymerization initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one) "Darocure 1173" (made by Chiba-Geigi Co., Ltd.) were mixed. This mixture was printed in the same manner as in Example 1, cured, and the spacer was placed on BM. Specifically, it was cured by irradiating 1000 mj / cm of ultraviolet rays. As a result, good characteristics were obtained.

Example 8

The same spacer particles (A) as in Example 3-2 were used. The functional group of particle | grains (A) is an epoxy group. As resin (B), "Epolite 828" (epoxy resin, the Japan epoxy resin company make) and "OXT-101" (3-ethyl-3-hydroxymethyl oxetane, the product made by Toagosei Co., Ltd.) are used, Photocationic polymerization initiator "acid aid SI-100L" (aromatic sulfonium salt compound) was mixed. This mixture was printed in the same manner as in Example 1, cured, and the spacer was placed on BM. Specifically, it was cured by irradiating with 1000 mj / cm of ultraviolet rays, followed by heat treatment at 150 ° C. for 30 minutes. As a result, the adhesiveness of resin and spacer particle improved, and liquid-crystal contamination was also suppressed.

Example 9

The same spacer particles (A) as in Example 3-2 were used. The functional group of particle | grain (A) is an epoxy group. As resin (B), alicyclic epoxy resin "GT301" (Diecel Kagaku Co., Ltd.) was used, and the photocationic polymerization initiator "acid aid SI-100L" (aromatic sulfonium salt type compound) was mixed. This mixture was printed in the same manner as in Example 1, cured, and the spacer was placed on BM. Specifically, it was cured by irradiating with 1000 mj / cm of ultraviolet rays, followed by heat treatment at 120 ° C. for 15 minutes. As a result, good characteristics were obtained.

Example 10

The same spacer particles (A) as in Example 2 were used. The functional group of particle | grains (A) is a hydroxyl group. As resin (B), "Epicoat 806" (bisphenol F type epoxy resin: Japan epoxy resin company) was used, and the photocationic polymerization initiator "acid aid SI-100L" (aromatic sulfonium salt type compound) was mixed. This mixture was printed in the same manner as in Example 1, cured, and the spacer was placed on BM. Specifically, it was cured by irradiating an ultraviolet ray of 1000mj / cm, followed by heat treatment at 120 ° C for 15 minutes. As a result, good characteristics were obtained.

Example 11

The same spacer particles (A) as in Example 3-2 were used. The functional group of particle | grains (A) is an epoxy group. As the resin (B), an epicoat 806 (bisphenol F type epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd.) was used, and a diluent (bifunctional epoxy resin `` Epicron 720 '' (neopentyl glycol diglycidyl ether, Dainippon Ink, Inc.) and the photo cationic polymerization initiator "San-Ade SI-100L (aromatic sulfonium compound). This mixture was printed in the same manner as in Example 1, cured, and spacers were placed on BM. Specifically, UV was irradiated at 1000mj / cm and then cured by heat treatment at 120 ° C. for 15 minutes, as a result, good characteristics were obtained.

Example 12

The same spacer particles (A) as in Example 3-2 were used. The functional group of particle | grains (A) is an epoxy group. As the resin (B), polycaprolactone tetraol epoxy resin having a partial COOH group was used. This resin is made to react methyl tetrahydro phthalic anhydride "Epolite B-570" (made by Dainippon Ink, Inc.) with "Fraccel 410D" (polycaprolactone tetraol, the Daicel Kagaku Kogyo Co., Ltd. make). Moreover, "Polyde GT403" (a polyfunctional alicyclic epoxy resin and the Daicel Kagaku Kogyo Co., Ltd.) was mixed. This mixture was printed in the same manner as in Example 1, cured, and the spacer was placed on BM. Specifically, the mixture was cured by heating at 180 ° C. for 60 minutes. As a result, good characteristics were obtained.

Example 13

The same spacer particles (A) as in Example 5 and an optical radical polymerization initiator were used, and as the resin (B), ultraviolet curable resin "M350" (trimetholpropane EO-modified triacrylate: manufactured by Toagosei Co., Ltd.) was used. In order to make it suitable viscosity for inkjet, it diluted with propylene glycol monomethyl ether and obtained the spacer particle dispersion liquid.

The obtained dispersion liquid was discharged to a board | substrate using a well-known inkjet apparatus, and it preliminarily dried at 120 degreeC for 30 minutes, and it hardened | cured by irradiating an ultraviolet-ray at 1000mj / cm, and after-baking was performed at 150 degreeC for 30 minutes.

(Comparative Example 1)

The same spacer particles (A) as in Example 1 were used. The functional group of particle | grains (A) is a hydroxyl group. As resin (B), polyester acrylate "M7100" (made by Toagosei Co., Ltd.) was used, and the high boiling point solvent (propylene glycol diacetate) and the photoradical initiator were mixed. This mixture was printed in the same manner as in Example 1, cured, and the spacer was placed on BM. Specifically, the mixture was heated at 80 ° C. for 10 minutes and then cured by irradiating with 1000 mj / cm of ultraviolet rays.

As a result, the adhesion between the spacer particles and the resin, the adhesion between the ink and the alignment film were low, light loss and gap deviation were observed, and liquid crystal contamination was also confirmed.

Example 14

The same spacer particles (A) as in Example 1 were used. The functional group of particle | grains (A) is a hydroxyl group. As resin (B), melamine polyester resin was used and the high boiling point alcohol solvent was mixed. This mixture was printed in the same manner as in Example 1, cured, and the spacer was placed on BM. Specifically, it was cured by heating at 210 ° C. for 60 minutes.

As a result, the adhesion between the spacer particles and the resin was good, the adhesion between the ink and the alignment film was slightly low, and light loss, gap deviation, and liquid crystal contamination were also slightly observed.

(Comparative Example 2)

The spacer particles used in Example 13 were changed to the particles used in Example 1. Other experiments were conducted in the same manner as in Example 13. As a result, the adhesiveness of spacer particle and binder resin was low, and impact resistance was low. The adhesion between the ink and the alignment film was slightly low, and light loss, gap deviation, and liquid crystal contamination were also slightly seen.

As described above, according to the present invention, the adhesion between the spacer particles and the binder resin can be improved in the spacer forming method by the printing method.

Claims (13)

As ink for spacer formation used in the printing method, A: spacer particles; And C: An ink for forming a spacer, comprising a thermosetting or active energy ray-curable resin mixture for dispersing the spacer particles. The ink according to claim 1, wherein the resin mixture (C) contains at least one component containing a functional group capable of chemical reaction with the particles (A). The said component is 1 type (s) or 2 or more types of resin (B) which has the functional group (b) which can react by heating, and the said particle | grain (A) is the functional group (a) which can react with the said functional group (b) Ink which has a. The ink according to claim 3, wherein the functional group (b) of the resin (B) is a functional group (b1) capable of reacting with a functional group remaining in the alignment film. The ink according to claim 4, wherein the functional group (b1) is an epoxy group, and the functional group (a) of the particle (A) is a functional group (a1) capable of reacting with an epoxy group. The said component is 1 type (s) or 2 or more types of resin (B) which has a functional group (b ') which can react with an active energy ray, and the said particle | grains (A) can react with the said functional group (b'). Ink which has a functional group (a '). The ink according to claim 6, wherein the resin mixture (C) contains a component having a functional group (b1 ') capable of reacting with a functional group remaining in the alignment film. The diluent (D) and / or the photo radical initiator (E) according to claim 6 or 7, wherein the resin mixture (C) has a functional group capable of reacting with the functional group (a ', b') or the functional group (b1 '). Ink containing a). The said component is 1 type or 2 or more types of resin (B) which has a functional group (b ") which can be cationicly polymerized by heating and / or an energy beam, The said particle | grains (A) are the said functional group (b" And a functional group (a ") capable of reacting with the ink. The ink according to claim 9, wherein said functional group (b ") of said resin (B) is a functional group (b1") capable of reacting with a functional group remaining on said alignment film. The said functional group (b1 ") of the said resin (B) is an epoxy group, The said functional group (a") of the said particle | grain (A) is a functional group (a1 ") which can react with an epoxy group, It is characterized by the above-mentioned. ink. The thing of any one of Claims 9-11 which has a diluent (D) and / or a photocationic initiator (E) which have a functional group which can react with the said functional group (a ") or the said functional group (b"). Featuring ink. The ink according to any one of claims 1 to 12, which contains substantially no solvent.

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